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The development of an efficient electrocatalyst for HMF oxidation to FDCA has been in the early stages. Herein, the NiNPs/GO-Ni-foam is fabricated as an electrocatalyst for FDCA production. However, the electrocatalytic performance of the untreated NiNPs/GO-Ni-foam is observed with moderate Faradaic efficiency (FE) (73.0%) and FDCA yield (80.2%). By electrochemically treating the NiNPs/GO-Ni-foam in an alkaline solution with positive potential at different treatment durations, the degree of NiOOH on metal surfaces is changed. The distinctive electrocatalytic activity obtained when using the different NiOOH degrees allows to understand the crucial impact of NiOOH species in HMF electrooxidation. Enhancing the portion of the NiOOH phase on the electrocatalyst surface improves electrocatalytic activity in terms of FE and FDCA yield up to 94.8±4.8% and 86.9±4.1%, respectively. Interestingly, as long as the NiOOH portion on the electrocatalyst surface is preserved or regenerated, the electrocatalyst performance can be intact even after several catalytic cycles. The theoretical study via density functional theory (DFT) also agrees with the experimental observations and confirms that the NiOOH phase facilitates the electrochemical transformation of HMF to FDCA through the HMFCA pathway, and the potential limiting step of the overall reaction is the oxidation of FFCA to FDCA.
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This study investigates the correlation between the biomedical and structural properties of Zn/Sr-modified Calcium Phosphates (ZnSr-CaPs) synthesized via the sol-gel combustion method. X-ray diffraction (XRD) analysis revealed the presence of Ca10(PO4)6(OH)2 (HAp), CaCO3, and Ca(OH)2 phases in the undoped sample, while the additional phase, Ca3(PO4)2 (ß-TCP) was formed in modified samples. X-ray absorption near-edge structure (XANES) analysis demonstrated the incorporation of Sr into the lattice, with a preference for occupying the Ca1 sites in the HAp matrix. The introduction of Zn, furthermore, led to the formation of ZnO and CaZnO2 species. The ZnSr-CaPs exhibited significant antibacterial activity attributed to the generation of reactive oxygen species by ZnO, the oxidation reaction of CaZnO2, and the presence of Sr ions. Cytotoxicity tests revealed a correlation between the variation in ZnO content and cellular viability, with lower ZnO concentrations corresponding to higher cell viability. Additionally, the cooperative effects of Zn and Sr ions were found to enhance the bioactivity of CaPs, despite ZnO hindering the apatite formation process. These findings contribute to the deep understanding of the diverse role in modulating the antibacterial, cytotoxic, and bioactive properties of ZnSr-CaPs, offering potential applications in the field of biomaterials.
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Post-coordination design on covalent organic frameworks (COFs) is an efficient strategy for elevating the photocatalytic activity of organic moiety. However, the rigid skeletons and densely layered stacking of two-dimensional (2D) COFs cannot be flexibly adapted for specific conformations of metal complexes, thereby impairing the metal-COF cooperation. Here, we adopt a solvothermal method to immobilize nickel(II) ions into a 2,2'-bipyridine-containing 2D COF, forming a stable coordination motif. Such the complex remarkably enhances the photocatalytic performance, giving an optimized H2 evolution rate of as high as 51 300â µmol h-1 g-1 , 2.5â times higher than the pristine COF. The evolved hydrogen gas can also be detected upon 700-nm light irradiation, while its analog synthesized by the traditional coordination method is photo-catalytically inert. This work provides a strategy for optimizing the metal-COF coordination system and strengthening a synergy for electronic regulation in photocatalysis.
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Metal phthalocyanines (MePc) hold great promise in electrochemical reduction of CO2 to value-added chemicals, whereas the catalytic activity of MePc-containing polymers often suffers from a limited molecular modulation strategy. Herein, we synthesize an ultrathin conjugated microporous polymer sheath around carbon nanotubes by an ionothermal copolymerization of CoPc and H2 Pc via the Scholl reaction. Given the H2 Pc-mediated regulation in the synthesis, CoII metal is well preserved in the form of single atoms on the polymer sheath of the carbon nanotubes. With the synergistic effect of H2 Pc moieties as proton/electron donors, the composites can selectively reduce CO2 to CO with a high Faradaic efficiency (max. 97 % at -0.9â V) in broad potential windows, exceptional turnover frequency (97 592â h-1 at -0.65â V) and large current density (>200â mA cm-2 ). It is thus desirable to develop a family of heterogeneous polymerized MePc with molecularly regulating electrocatalytic activity.
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A well designed compact furnace has been designed for in situ X-ray absorption spectroscopy (XAS). It enables various heat ramps from 300â K to 1473â K. The furnace consists of heaters, a quartz tube, a circulated refrigerator and a power controller. It can generate ohmic heating via an induction process with tantalum filaments. The maximum heating rate exceeds 20â Kâ min-1. A quartz tube with gas feedthroughs allows the mixing of gases and adjustment of the flow rate. The use of this compact furnace allows in situ XAS investigations to be carried out in transmission or fluorescence modes under controlled temperature and atmosphere. Moreover, the furnace is compact, light and well compatible to XAS. The furnace was used to study cationic oxidation states in Pr6O11 and NiO compounds under elevated temperature and reduced atmosphere using the in situ X-ray absorption near-edge structure (XANES) technique at beamline 5.2 SUT-NANOTEC-SLRI of the Synchrotron Light Research Institute, Thailand. At room temperature, Pr6O11 contains a mixture of Pr3+ and Pr4+ cations, resulting in an average oxidation state of +3.67. In situ XANES spectra of Pr (L3-edge) show that the oxidation state of Pr4+ cations was totally reduced to +3.00 at 1273â K under H2 atmosphere. Considering NiO, Ni2+ species were present under ambient conditions. At 573â K, the reduction process of Ni2+ occurred. The Ni0/Ni2+ ratio increased linearly with respect to the heating temperature. Finally, the reduction process of Ni2+ was completely finished at 770â K.
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Hydrazine is a common reducing agent widely used in many industrial and chemical applications; however, its high toxicity causes severe human diseases even at low concentrations. To detect traces of hydrazine released into the environment, a robust sensor with high sensitivity and accuracy is required. An electrochemical sensor is favored for hydrazine detection owing to its ability to detect a small amount of hydrazine without derivatization. Here, we have investigated the electrocatalytic activity of layered birnessite manganese oxides (MnO2) with different intercalants (Li+, Na+, and K+) as the sensor for hydrazine detection. The birnessite MnO2 with Li+ as an intercalant (Li-Bir) displays a lower oxidation peak potential, indicating a catalytic activity higher than the activities of others. The standard heterogeneous electron transfer rate constant of hydrazine oxidation at the Li-Bir electrode is 1.09- and 1.17-fold faster than those at the Na-Bir and K-Bir electrodes, respectively. In addition, the number of electron transfers increases in the following order: K-Bir (0.11 mol) < Na-Bir (0.17 mol) < Li-Bir (0.55 mol). On the basis of the density functional theory calculation, the Li-Bir sensor can strongly stabilize the hydrazine molecule with a large adsorption energy (-0.92 eV), leading to high electrocatalytic activity. Li-Bir also shows the best hydrazine detection performance with the lowest limit of detection of 129 nM at a signal-to-noise ratio of â¼3 and a linear range of 0.007-10 mM at a finely tuned rotation speed of 2000 rpm. Additionally, the Li-Bir sensor exhibits excellent sensitivity, which can be used to detect traces of hydrazine without any effect of interference at high concentrations and in real aqueous-based samples, demonstrating its practical sensing applications.
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A photoelectrochemical (PEC) cell can split water into hydrogen and oxygen with the assistance of solar illumination. However, its application is still limited by excessive bulk carrier recombination and sluggish surface oxygen evolution reaction (OER) kinetics. Taking SnS2 as an example, a promising layered optoelectronic semiconductor, Ar plasma treatment strategy was used to introduce a SnS/SnS2 P-N heterojunction and O-S bond near the surface of a SnS2 nanosheet array, simultaneously increasing the separation efficiency of photogenerated electron-hole pairs in the bulk and lowering the OER overpotential at the surface. The onset potential of the plasma-treated SnS2 nanosheet array shifts negatively to 0.16â V, and the photocurrent density at 1.23â V vs. RHE boosts to 2.15â mA cm-2 , which is 7 times that of pristine SnS2 . This work demonstrates a facile plasma treatment strategy to modulate the energy band structure and surface chemical states for improved PEC performance.
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The SUT-NANOTEC-SLRI beamline was constructed in 2012 as the flagship of the SUT-NANOTEC-SLRI Joint Research Facility for Synchrotron Utilization, co-established by Suranaree University of Technology (SUT), National Nanotechnology Center (NANOTEC) and Synchrotron Light Research Institute (SLRI). It is an intermediate-energy X-ray absorption spectroscopy (XAS) beamline at SLRI. The beamline delivers an unfocused monochromatic X-ray beam of tunable photon energy (1.25-10â keV). The maximum normal incident beam size is 13â mm (width) × 1â mm (height) with a photon flux of 3 × 108 to 2 × 1010â photons s-1 (100â mA)-1 varying across photon energies. Details of the beamline and XAS instrumentation are described. To demonstrate the beamline performance, K-edge XANES spectra of MgO, Al2O3, S8, FeS, FeSO4, Cu, Cu2O and CuO, and EXAFS spectra of Cu and CuO are presented.
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The workability of fresh Portland cement (PC) concrete critically depends on the reaction of the cubic tricalcium aluminate (C3A) phase in Ca- and S-rich pH >12 aqueous solution, yet its rate-controlling mechanism is poorly understood. In this article, the role of adsorption phenomena in C3A dissolution in aqueous Ca-, S-, and polynaphthalene sulfonate (PNS)-containing solutions is analyzed. The zeta potential and pH results are consistent with the isoelectric point of C3A occurring at pH â¼12 and do not show an inversion of its electric double layer potential as a function of S or Ca concentration, and PNS adsorbs onto C3A, reducing its zeta potential to negative values at pH >12. The S and Ca K-edge X-ray absorption spectroscopy (XAS) data obtained do not indicate the structural incorporation or specific adsorption of SO42- on the partially dissolved C3A solids analyzed. Together with supporting X-ray ptychography and scanning electron microscopy results, a model for C3A dissolution inhibition in hydrated PC systems is proposed whereby the formation of an Al-rich leached layer and the complexation of Ca-S ion pairs onto this leached layer provide the key inhibiting effect(s). This model reconciles the results obtained here with the existing literature, including the inhibiting action of macromolecules such as PNS and polyphosphonic acids upon C3A dissolution. Therefore, this article advances the understanding of the rate-controlling mechanism in hydrated C3A and thus PC systems, which is important to better controlling the workability of fresh PC concrete.
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The rational design of isolated metals containing zeolites is crucial for the catalytic conversion of biomass-derived compounds. Herein, we explored the insertion behavior of the isomorphic substitution of Ti(IV) in different zeolite frameworks, including ZSM-35 (FER), ZSM-5, and BEA. The different aluminium topological densities of each zeolite framework lead to the creation of different degrees of vacant sites for hosting the tetrahedrally coordinated Ti(IV) active sites. These observations show the precise control of the degree of four-coordinated Ti(IV) sites in a zeolite framework, especially in BEA topology, by tuning the degree of unoccupied sites in the host zeolite structure via dealumination. Interestingly, the more vacancies in the host zeolite structure, the more isolated tetrahedrally coordinated Ti(IV) can be increased, eventually enhancing the catalytic performance in methyl oleate (MO) epoxidation for producing methyl-9,10-epoxystearate (EP). The engineered Ti-ß exhibits outstanding performances in bulky MO epoxidation with the amount of produced EP per number of Ti sites up to 17.1 ± 1.8 mol mol-1. This observation discloses an alternative strategy for optimizing catalyst efficiency in the rational design of the Ti-embedding zeolite catalyst, endeavoring to reach highly efficient catalytic performance.
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Metal single-site catalysts have recently played an essential role in catalysis due to their enhanced activity, selectivity, and precise reaction control compared to those of conventional metal cluster catalysts. However, the rational design and catalytic application of metal single-site catalysts are still in the early stages of development. In this contribution, we report the rational design of Fe single sites incorporated in a hierarchical ZSM-5 via atomic layer deposition (ALD). The designer catalysts demonstrated highly dispersed Fe species, predominantly stabilized by oxygen atoms in the zeolite framework at terminal, isolated, and vicinal silanol groups within the micropores and external surfaces of the zeolite. The successful incorporation of highly thermally stable and uniform Fe single sites into hierarchical zeolite through ALD represents a significant advancement in few-walled carbon nanotube production. The inner and outer diameters of produced CNTs are approximately 4.4 ± 2.4 and 8.6 ± 1.8 nm, respectively, notably smaller than those produced via traditional impregnated catalysts. This example emphasizes the concept of rational design of a single Fe site dispersed on a hierarchical ZSM-5 surface, which is anticipated to be a promising catalyst for advancing catalytic applications.
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Although being transition metals, the Fenton-inactive group 3-4 elements (Sc, Y, La, Ti, Zr, and Hf) can easily lose all the outermost s and d electrons, leaving behind ionic sites with nearly empty outermost orbitals that are stable but inactive for oxygen involved catalysis. Here, it is demonstrated that the dynamic coordination network can turn these commonly inactive ionic sites into platinum-like catalytic centers for the oxygen reduction reaction (ORR). Using density functional theory calculations, a macrocyclic ligand coordinated yttrium single-atom (YN4 ) moiety is identified, which is originally ORR inactive because of the too strong binding of hydroxyl intermediate, while it can be activated by an axial ligand X through the covalency competition between YX and YOH bonds. Strikingly, it is also found that the binding force of the axially coordinated ligand is an effective descriptor, and the chlorine ligand is screened out with an optimal binding force that behaves self-adaptively to facilitate each ORR intermediate steps by dynamically changing its YCl covalency. These experiments validate that the as-designed YN4 -Cl moieties embedded within the carbon framework exhibit a high half-wave potential (E1/2 = 0.85 V) in alkaline media, the same as that of the commercial Pt/C catalyst .
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Rechargeable aqueous zinc-ion batteries (AZIBs) are attracting much attention as high-density energy storage systems owing to their fascinating features with low cost, high safety, and simple manufacturing process. However, the commercialization of Zn anodes is hindered by uncontrollable dendrite growth and water-induced side reactions. Herein, a spontaneous reconstruction of a honeycomb-structural hopeite layer (ZPO) on a Zn metal anode (Zn@ZPO) is rationally developed as a functional protection interface by the liquid-phase deposition strategy. The formed ZPO layer not only promotes ion/charge transport and restrains Zn corrosion but also modulates the preferred deposition orientation of the Zn(002) nanosheet for the dendrite-free Zn anode. Accordingly, the Zn@ZPO symmetric cell exhibits satisfactory cycle lifespans of 1500 h at 1 mA·cm-2/1 mAh·cm-2 and 1400 h at 5 mA m-2/1 mAh·cm-2. When assembled with the (NH4)2V10O25·8H2O (NVO) cathode, the Zn@ZPO||NVO full cell delivers an ultrastable cycling lifespan for 25â¯000 cycles with a discharge capacity retention of 86.6% at 5 A·g-1. Therefore, this work will pave a novel avenue for constructing dendrite-free AZIBs.
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5-Hydroxymethylfurfural (5-HMF) synthesized through glucose conversion requires Lewis acid (L) site for isomerization and Brønsted acid (B) site for dehydration. The objective of this work is to investigate the influence of the metal type of Al-SBA-15-supported phosphates of Cr, Zr, Nb, Sr, and Sn on glucose conversion to 5-HMF in a NaCl-H2 O/n-butanol biphasic solvent system. The structural and acid property of all supported metal phosphate samples were fully verified by several spectroscopic methods. Among those catalysts, CrPO/Al-SBA-15 provided the best performance with the highest glucose conversion and 5-HMF yield, corresponding to the highest total acidity of 0.65â mmol/g and optimal L/B ratio of 1.88. For CrPO/Al-SBA-15, another critical parameter is the phosphate-to-chromium ratio. Moreover, DFT simulation of glucose conversion to 5-HMF on the surface of the optimized chromium phosphate structure reveals three steps of fructose dehydration on the Brønsted acid site. Finally, the optimum reaction condition, reusability, and leaching test of the best catalyst were determined. CrPO/Al-SBA-15 is a promising catalyst for glucose conversion to high-value-added chemicals in future biorefinery production.
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In nature, the oxygen reduction reaction (ORR) is catalyzed by cytochrome P450 (CYP) enzymes containing heme iron centers with an axial thiolate ligand (FeN4 -S), which are among the most finely developed catalysts by natural selection. However, the exceptional ORR activity and selectivity of CYP enzymes originate from their non-rigid and self-adaptive coordination network with molecular ligands, which sacrifices the stability of the active motifs under electrochemical reaction conditions. Here, a design strategy to circumvent this dilemma by incorporating Fe-N4 motifs into carbon matrices instead of the protein scaffold and replacing the axial molecular thiolate ligand with a stable tellurium cluster (Ten ) is demonstrated. Theoretical calculations indicate a moderate interaction between Fe 3d and Te 5p orbitals once n > 2, allowing the FeTe bond to dynamically change its strength to adaptively facilitate the intermediate steps during the ORR process, which renders FeN4 -Ten active sites with superior ORR activity. This adaptive behavior mimics the conformational dynamics of an enzyme during the reaction, but retains the stability nature as a heterogeneous catalyst. The experiments validate that the as-designed catalyst with a characterized FeN4 -Ten structure outperforms the commercial Pt/C catalyst both on activity and stability.
Assuntos
Metaloides , Telúrio , Ligantes , Oxirredução , Oxigênio/químicaRESUMO
In this research, we investigate the stability of a Li-ion cathode created by mixing a borate based glass which has been doped with Ni/Co and vanadium pentoxide (V2O5). V2O5 has a high specific capacity in battery systems because of its layered structure and variety of oxidation states. However, due to the flimsy structure, the capacity stability of V2O5 is fairly low. In this case, we seek to overcome the problem by mixing Ni/Co-doped borate based glass. The voltage-capacity graph demonstrates that the form of the glass mix was changed from a stairway shape to a straight line while the capacity was not much decreased. The crystallography study using X-ray diffractograms looked at whether the cycling test had changed the crystal structure of V2O5. The X-ray Absorption Near Edge Structure (XANES) results also reveal that V2O5's oxidation state changed from V5+ to V4+. The glass mix can retain more of the V5+ state, indicating that glass mixture helps to release the Li-ions trapped in the structure. The findings of this study might contribute to the rapid advancement of renewable energy and electric vehicle technology.
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Magnetite (Fe3O4) and goethite (α-FeOOH) were synthesized via a hydrothermal approach and utilized as adsorbents for Cr6+ removal in an aqueous medium. The typical crystal structures of the synthesized Fe3O4 and α-FeOOH were confirmed by XRD and TEM. Fe3O4 in a spherical shape with a surface area of 32 m2 g-1 was established. While α-FeOOH had a rod-like form with a larger surface area of 84 m2 g-1. Cr6+ removal in an aqueous solution was studied in various conditions to evaluate thermodynamic and kinetic parameters. The adsorption isotherms on both adsorbents fit the Langmuir model indicating monolayer adsorption. Fe3O4 showed a better adsorption ability than α-FeOOH even though it had a lower surface area. XAS and XPS analysis strongly evidenced the production of stable Cr3+ species of Fe(1-x)Cr x OOH and Fe(3-x)Cr x O4 by Cr6+ reduction and migration processes into the bulk structure. Thus, the existence of stable Cr-species in Fe3O4 structure strongly affected Cr-adsorption ability rather than the surface area of the adsorbent. However, the precipitated Cr2O3 and HCrO4 - molecules electrostatically adsorbed on the outer surface of α-FeOOH without bulk transformation. The presence of physisorbed FeO-HCrO4 species on α-FeOOH led to low reducibility and adsorption capability of Cr6+.
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CuFe2O4 spinel oxide has attracted research interest because of its versatile practical applications, especially for catalysis. In this study, nanometre-sized CuFe2O4 particles were prepared by three different methods, including nanospace confinement in SBA-15, hard template removal, and sol-gel combustion. The relationship between structure, size, magnetic behaviour, and reducibility of the catalysts was further investigated by various advanced techniques. Samples prepared by impregnation and hard template removal show high surface area and small crystallite size with superparamagnetic behaviour. In contrast, the sol-gel sample exhibits ferromagnetic properties with a large crystallite size and low surface area. Although all samples present a tetragonal crystal structure, the distributions of Fe and Cu cations in tetrahedral and octahedral sites in the spinel structure are different. The reducibility results demonstrate that the supported CuFe2O4/SBA-15 shows the lowest reduction profile. These results could suggest that the synthesis method strongly affects the crystal properties and cation distribution in the spinel structure, microstructure, surface area and reducibility, which are among the most relevant physicochemical properties for the catalytic activity.
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In this work, a simple, facile growth approach for a vertically aligned ZnO thin film is fabricated and its application towards methane gas sensors is demonstrated. ZnO thin film was prepared by a combination of hydrothermal and sputtering methods. First, a ZnO seed layer was prepared on the substrate through a sputtering technique, then a ZnO nanorod was fabricated using a hydrothermal method. The surface morphology of the ZnO film was observed by scanning electron microscopy (SEM). A ZnO nanorod coated on the dense seed layer is clearly visible in the SEM image. The average size of the hexagonal-shaped ZnO rod was around 50 nm in diameter, with a thickness of about 1 mm. X-ray absorption near-edge structures (XANES) were recorded to characterize the structural properties of the prepared film. The obtained normalized Zn K-edge XANES of the film showed the characteristic features of ZnO, which agreed well with the standard ZnO sample. The measurement of Zn K-edge XANES was performed simultaneously with the sensing response. The results showed a good correlation between sensor response and ZnO structure under optimal conditions.
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We present the investigation of the roles of molybdenum (Mo) dopant with a concentration of 0.0625% to 1.0% Mo into bismuth tungstate (Bi2WO6) by a one-step hydrothermal method for the enhancement of photocatalytic activities. The obtained materials and doping effects were characterized by the morphology, crystal structure, chemical states, and optical properties. By combining XRD, XANES, and EXAFS studies, the distortion of the local structure with substitutional doping was revealed as doping with Mo ions was located at the lattice sites of the tungsten ions. Photocatalytic reactions of Mo-doped Bi2WO6 were studied by the degradation of methyl orange dye under visible light irradiation. The results show that the optimal concentration of Mo dopant is 0.25%, with the highest photocatalytic activity up to â¼2-fold compared to the bare Bi2WO6. From our investigation, we propose that the impurity level is located below the conduction band edge of Bi2WO6 after doping with Mo6+ ions. This impurity level acts as an electron trapping site to prevent the transition of excited electrons from the conduction band to the valence band. By trapping experiments, the superoxide anion radicals (O2Ë-) as the main active species to enhance photocatalytic efficiency was established.